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NEW  REACTIONS  OF  AROMATIC  ARSINES 


BY 


lOSEPH  LOWE  HALL 

B.  S.  University  of  Illinois,  1919 
M.  S.  University  of  Illinois,  1921 


• THESIS 

SUBMITTED  IN  PARTIAL  FULFILLMENT  OF  THE  REQUIREMENTS 
FOR  THE  DEGREE  OF  DOCTOR  OF  PHILOSOPHY  IN  CHEMISTRY 
IN  THE  GRADUATE  SCHOOL  OF  THE  UNIVERSITY 
OF  ILLINOIS,  1922. 


URBANA,  ILLINOIS 


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UNIVERSITY  OF  ILLINOIS 


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I HEREBY  RECOMMEND  THAT  THE  THESIS  PREPARED  UNDER  MY 

SUPERVISION  BY Tosg-ph  Lowe  -Hall 

ENTITLED  ppA"'VTr>TO  nv  ApnUA  ttp  a pc  timer 


BE  ACCEPTED  AS  FULFILLING  THIS  PART  OF  THE  REQUIREMENTS  FOR 
THE  DEGREE  OF  Doctor  of  PLl 


Recommendation  concurred  in* 


Committee 


on 

Final  Examination* 


^Required  for  doctor’s  degree  but  not  for  master’s 


CONTENTS 


A c ImoY/ le  dginen  t 

Introduction 1 

Historical 3 

Theoretical 10 

Experimental.  . 16 

A.  Preparation  of  Phenylarsine 16 

B.  Reactions  with  Phenylarsine 21 

C.  Reactions  v/ith  Phenylarsine-Grignard  Complex 26 

Summary , 38 

Bibliography.  . 39 

Vita 40 


I 


'll-'" 


ACEMOWLEDG!/lSNT 


This  investigation  has  been  carried  out  under  the  direction 
and  supervision  of  Professor  Roger  Adams,  to  whom  the  writer 
v/ishes  to  express  sincere  gratitude  for  his  genereus  and 
capable  assistance. 


Digitized  by  the  Internet  Archive 
in  2015 


https://archive.org/details/newreactionsofarOOhall 


INTRODUCTION 


1 


Investigation  of  arsenic  compounds  has  recently  been  stimulated 
by  a government  appropriation  for  university  fellowships  to  be 
awarded  and  supervised  by  the  United  States  Interdepartmental 
Social  Hygiene  Board,  The  purpose  of  the  investigational  v/ork 
has  been  to  develop  new  types  of  compounds  of  arsenic  in  the  hope 
of  finding  substances  of  therapeutic  value  in  combatting  venereal 
diseases.  Various  kinds  of  arsenical  drugs  have  been  developed 
and  used  since  1902,  when  Bechamp's  compound  "atoxyl"  began  to 
be  tried  in  therapeutics.  Tv/o  of  the  most  successful  and  most 
widely  used  of  these  compounds  are  "Salvarsan"  and  "Neosalvarsan" , 
which  is  the  sodium  methylene -sulfinate  of  salvarsan.  Both  of 
these  compounds  v/ere  discovered  by  Ehrlich,  who  did  a vast  amount 
of  research  in  arsenical  drugs.  Compounds  containing  arsenic  in 
an  available  state  for  proper  assimilation  in  the  body  appear  to 
exert  a specific  reaction  against  diseases  of  protozoal  origin. 

One  of  the  serious  problems  is,  of  course,  to  reduce  the  toxicity 
of  the  arsenic  so  that  its  use  will  not  be  dangerous. 

The  purpose  of  this  investigation  has  been  to  carry  out  re- 
actions with  phenyl-arsine  which  might  be  analogous  to  those  of 
its  nitrogen  analogue,  aniline.  The  arsines  form  a series  of 
compounds  v/hich  is  very  complete  in  its  analogy  with  the  amines 
as  far  as  structure  is  concerned“-prima2->y , secondary,  tertiary, 
aliphatic,  and  aromatic  types — but  the  chemical  analogy  is  not 
so  close.  C,  S.  Palmer  (1)  found  that  phenyl  arsine  condenses 
with  benzaldehyde  and  butyraldehyde  v;ith  the  formation  of 
compounds  corresponding  somewhat  to  aldehyde  ammonias,  except  that. 


2 

whereas  only  one  hydrogen  on  the  nitrogen  reacts  in  the  formation 

of  aldehyde  ammonia,  both  hydrogens  on  the  arsenic  react  each 

v/ith  one  mol  of  the  aldehyde;  a compound  of  the  type  CHOII)  i^sR 

6 5 2 ' 

is  formed. 

The  present  investigation  has  been  concerned  with  the  further 
study  of  reactions  which  are  typical  of  the  amines  in  their 
application  to  the  arsines,  particularly  reactions  with  acid 
chlorides,  anhydrides,  and  esters,  nitroso  compounds,  and  C-rig- 
nard  reactions. 


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II.  HISTORICAL 

The  discovery  of  the  first  organic  compound  of  arsenic  is 
accredited  to  Cadet,  who  in  1760  obtained  on  distilling  arsenic 
trioxide  with  potassium  acetate,  a heavy,  fuming  liquid  easily 
inflammable  in  the  air  and  of  a very  offensive  odor.  The  arsenic 
compomids  which  are  thus  formed  are  cacodyl  and  cacodyl  oxide, 
cacodyl  being  spontaneously  inflammable. 

Palmer  (2)  prepared  the  first  secondary  arsine  by  the  reduction 
of  cacodyl  chloride  by  means  of  platinized  zinc  and  hydrochloric 
acid  in  alcoholic  solution.  Lehn  and  V/ilcox  (3),  however, 
found  that  it  v;as  unnecessary  to  prepare  cacodyl  chloride  from 
cacodyl  oxide  and  mercuric  chloride  for  this  reduction;  they 
found  that  the  direct  reduction  of  cacodyl  and  cacodyl  oxide  took 
place  as  well  as  that  of  the  chloride,  and  therefore  used  for 
this  purpose  the  above-mentioned  "Cadet's  fuming  arsenical  liquid." 

Palmer  and  Dehn  also  prepared  the  first  primary  arsine,  mono- 
methylarsine , by  reducing  methyldichlorlrsine ; they  found  the 
reduction  of  methylarsonic  acid,  hov/ever,  to  be  much  more  con- 
venient. These  investigators  encountered  difficulties  because 
of  the  extreme  volatility  of  the  product  and  its  gr^eat  avidity 
for  o:cygen.  In  the  same  communication  they  announce  the  dis- 
covery of  the  first  aromatic  primary  arsine,  phenylarsine . 

(Various  reactions  of  this  compound  are  the  basis  of  the  author's 
present  investigation).  Palmer  prepared  phenylarsine  by  the 
reduction  of  calcium  phenylarsonate  with  amalgamated  zinc  dust 
and  hydrochloric  acid.  The  reduction  v/as  earried  on  in  a flask 
equipped  with  a reflux  condenser,  in  the  top  of  which  was  fitted 

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4 

a dropping  funnel  and  a bent  tube  dipping  into  mercury  to  serve 
as  an  air  trap  in  allowing  the  escape  of  the  excess  hydrogen. 
Hydrochloric  acid  v/as  slowly  admitted  througli  the  dropping  funnel. 
The  reaction  mixture  was  covered  with  a layer  of  ether  to  take 
up  the  phenylarsine  as  it  v;as  formed,  it  being  very  insoluble  in 
v/ater.  Essentially  this  same  method  is  yet  employed  in  this 
laboratory,  using,  however,  the  free  phenylar sonic  acid.  Palmer 
mentions  tv/o  ways  in  V7hich  the  phenylarsonic  acid  maybe  prepared: 
First,  that  of  La  Coate  and  Michaelis  (5)  in  v/hich  the  phenyl- 
arsine dichloride  is  prepared  from  mercury  diphenyl  according  to 
the  equation: 

'Hg(CgH5)2  t 2 AsCl^  = 2 CgllgAsClg  HgClg 

The  conversion  of  this  product  to  phenylarsonic  acid  is  evident 
from  the  equations: 

CgH5AsCl2  t Clg  = CgHgAsCl^ 

CgH5AsCl4  t 3 H2O  = CgH5As0(0H)2-J-  4 HCl^ 

The  second  and  better  m.ethod  was  that  of  I-.ichaelis  and  Loesner  (6) 
in  ViThich  the  phenylarsine  dichloride  v/as  prepared  according  to 
the  following  equations: 

AsClj  t 3 CgHgCl  t 6 Ha  s {CQE^)^ks  ‘ 6 HaCl 

^^6^5^ 3“^®  t 2 AsClj  (heat  in  closed  tube)  = 3 C0HgAsCl2 

The  m.ethod  now  used  in  this  laboratory  for  the  preparation 
of  phenylarsonic  acid  is  that  described  by  Norris  (7)  which  will 
be  discussed  under  the  experimental  part. 

According  to  Dehn  (8)  the  methyl  and  ethyl  amines  are  10,000 
to  15,000  times  more  soluble  in  water  than  the  analogous  arsines, 
v/hich  are  only  about  one  part  soluble  in  ten  thousand  parts  of 


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v/afer’  at  25°.  The  s.olnbill1-y  Increases  with  the  increase  of 
basicity.  Dehn  observed  that  the  odor  of  dilute  phenylars3.ne 
resembles  that  of  hyacinths.  The  author,  however,  fails  to  re- 
cognize any  such  reseirb lance  and  is  inclined  to  believe  that  if 
such  existed,  florists  would  find  a market  for  hyacinths  only 
to  those  with  either  a perverted  sense  of  smell,  or  none  at  all. 

Phenylarsine  is  a transparent,  colorless,  highly  refractive, 
heavy  oil,  which  boils  at  148°  at  760  mm.,  93°  at  70  mm.,  84®  at 
55  mm.,  and  77  at  33  mm.  -^t  is  insoluble  in  water,  soluble  in 
alcohol,  ether,  and  carbon  disT-ilfide.  In  air  it  ¥/arms  rapidly 
and  changes  to  a light  yellov/,  plastic  mass.  Three  products 
result  from  the  oxidation  as  indicated  by  the  follov\ring  equations: 
C0H5ASH2  -!■  O2  = C0H5ASO  t H2O 
C0K5ASH2  t 3 0 = C0H5AsO(OE)2 
2 CgH^AsHg  t O2  = CgHgAsiAsCgHg  * 2 H20^ 

Phenylarsine  reacts  with  nitric  acid  v^ith  explosive  violence 
to  yield  products  as  indicated  by  the  equations: 

C0H5ASH2  t 6 HNO3  = C0H5AsO(OH)2  t 3 H2O  t 6 NO2 
2 CgH^AsHg  t 4 HlIO^  = CgH^As  :AsCgH^  t 4 HgO  t 4 NOg 
2 CgH^AsHg  t 14  HNO3  = 2 CgHgNOg  t AsgO^  t 9 HgO  t 12  NOg 

Phenylarsine  reacts  with  bromine  in  various  steps  as  shown 
by  the  equations: 

CgH^AsHg  t Brg  z CgH^AsHBr .HBr 

CgHgAsHBr  t Br2  = CgH^AsBrg.HBr 

C0H5AsBr2  t Br2  =:  C0H5Br  t AsBr^ 

Similar  reactions  with  iodine  occur: 


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Dehn  also  finds  (9)  that  phenylarsine  is  unchanged  when 
heated  two  hours  in  a sealed  tube  at  180°,  but  after  heating 
three  hours  at  510^  decomposition  takes  place  according  to  the 
equation: 

3 C0H5ASH2  r (C0li0)2As  t 2 As  t 3 Hg 

This  reaction  demonstrates  the  unstable  linkage  of  the  hydrogen 
to  the  arsenic  and  explains  in  a measure  the  tendency  of  phenyl- 
arsine to  act  as  a reducing  agent  wherever  possible  rather  than 
to  condense  in  a manner  analogous  to  aniline.  This  tendency  will 
be  discussed  in  the  experim.ental  part. 

Dehn  (3)  observes  that  aliphatic  secondary  arsines  have 
greater  affinity  for  oxygen  than  primary  arsines,  the  affinity 
increasing  with  the  number  of  alkyl  groups  introduced;  the  se- 
condary and  tertiary  arsines  are  spontaneously  inflammable. 

Dime thy lar sine  reacts  easily  with  halogens,  halogen  a elds , and 
their  heavy  metal  salts,  v/ith  oxygen  and  sulfur,  oxides  and 
sulfides,  and  with  oxygenated  acids  and  salts.  Reactions  with 
halogens,  halogen  acids,  and  alkyl  halides  begin  with  a direct 
addition  forming  a pentavalent  arsenic,  followed  by  a molecular 
cleavage  leaving  a trivalent  arsenic.  Dime  thy lar s ine  gives  a 
wide  variety  of  products  on  oxidation  with  pure  or  atmospheric 
oxygen,  as  shown  by  the  equations: 

1.  6 (CH2)gAsH  t 3 Og  ~ ( CHgA s ) ^A s gOg  ^ 4 ^2^6  ^ ^ ^2^ 

2.  4 (CH3)2AsH  t Og  : 4 (CHjAs)^  t 2 CgHg  <•  2 HgO 

3.  4 (CH3)2AsH  O2  : AS2  t 4 C2H0  t 2 H2O 


7 


4.  2 (CH5)2AsH  t 9 Og  z t 4 COg  t 7 HgO 

5.  4 (CH2)gAsH  t Og  = 2 ((CH2)As)g  t 2 HgO 

6.  2 (CH2)gAsE  t Og  = ((CH2)As)gO  t HgO 

7.  (CH3)2AsH  t Og  z (CH3)2As00H 

The  aromatic  secondary  arsines  are  obtained  by  reduction  of 
the  corresponding  arsinic  acids  with  apparently  the  same  ease 
as  the  aliphatic  secondary  arsines,  Dehn's  method  (3)  of  prepar 
ing  diphenyl  arsinic  acid  is  designed  to  obviate  the  use  of  mer- 
cury diphenyl  in  the  method  of  La  Coste  and  Michaelis  with  its 
inconvenience  and  poor  yields.  The  procedure  is  sim.ply  an 
adaptation  of  the  method  of  Michaelis  and  Loesner  with  the 
addition  of  an  ingenious  operation  for  the  isolation  of  the 
desired  product.  The  reactions  are  carried  out  according  to 
the  equations;  (the  first  being  nedrly  quantitative) 

3 CgHgCl  t AsCl^  t 6 Ka  = (CgHg)3As  t 6 NaCl 

2 (CgHg^^s  t ASCI3  (30  hours  at  22Q<=>)  z 3 (CgH5)2AsCl 

Water  is  added  to  the  reaction  mixture  and  chlorine  is  passed 
into  it,  whereupon  the  following  reactions  take  place  vifith  the 
various  constituents  present; 

1.  ASCI3  r 4 H2O  t CI2  = H3ASO4  r 5 HCl 

2.  CgH^AsClg  t 3 HgO  t Clg  = CgH^AsO^Hg  t 4 HCl 

3.  (CgHg)gAsCl  t 2 HgO  t Clg  = (CgHg)gAsOOH  t 3 HCl 

4.  (CgH^)3As  . HgO  » Clg  = t 2 HCl 


The  product  of  the  fourth  reaction  is  insoluble  in  v^ater  and 
may  be  filtered  from  the  hot  solution,  in  which  the  others  are 
soluble.  On  the  addition  of  magnesia  mixture  in  the  cold,  the 


8 


product  of  the  first  reaction  readily  comes  down,  and  on  boiling 
likev/ise  the  product  of  the  second  reaction  precipitates,  but 
not  the  third,  which  may  then  be  separated  by  filtration. 

7,'hen  the  filtrate  is  acidified  the  diphenylarsinic  acid  is  pre- 
cipitated, as  it  is  very  sli^tly  soluble  in  v;ater  at  room  temi- 
perature . Dehn  used  a system  of  this  sort  for  analysis  to  de- 
termine the  degree  of  substitution  in  arsines  and  their  d.erivatives 
He  also  found  an  application  of  the  Volhard  titration  for  halo- 
gens quite  applicable  to  halogen  substituted  arsines  such  as 
phenylarsine  dichloride,  tetraethyl  arsonium  iodide,  etc.  The 
product  was  boiled  up  v/ith  standard  silver  nitrate,  and  the 
excess  titrated  with  potassium  thiocyanate,  using  ferric  alum  as 
an  indicator.  The  preparation  of  diphenylarsinic  acid,  hov/ever, 
was  developed  much  more  efficiently , in  Germany  during  the  war 
(Morris),  as  it  v/as  an  intermediate  in  the  mianTifacture  of  di- 
phenyl chlorarsine  (blue  cross).  The  preparation  v;as  carried 
out  according  to  the  equations: 

CgHgNgCl  ^ Na^AsOj  s C0H^AsOgNa2  ^ NaCl  * Ng 

CgH^AsOjNag  t 2 HCl  = CgH^AsO^Hg  t 2 NaCl 
C0H0AsOgH2  t ^ ^^2^  ” * ^2^^4 

C0HgAsOgNa2  t C0H^N2C1  = { CgHg)2As0gNa  t NaCl  t Ng 

Numerous  German  patents  have  appeared  in  the  last  ten  years 
involving  reactions  of  aromatic  arsines.  Primary  arsines  v;ere 
found  to  react  (10)  with  arsenoxides  or  chlorides  vjith  the 
splitting  out  of  a molecule  of  water  or  tv/o  molecules  of  hydro- 
chloric acid.  Thus  it  is  possible  to  make  asymmetric  substi- 
tuted arsenobenzenes  of  the  general  type,  R’AsrAsR".  Pro- 


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9 


cesses  for  the  production  of  this  type  of  coiiipounds  are  covered 
by  other  patents  (11)  (12)  (13)  which  involve  methods  for  the 
simltane ous  reduction  of  arsonic  acids  or  oxides  of  tv/o  different 
types.  For  instance  upon  the  rediiction  of  two  arsonic  acids 
together  in  equimolecular  amounts,  R’As0(0H)2  ahd  R”As0(0iI)2^  an 
unsymnietrical  arsenobenzene  derivative  is  obtained,  R’As:AsR'*, 

It  has  been  fomid  (14)  that  compounds  containing  arsenic 
linked  to  phosphorus,  arsenic,  antimony,  tellurium,  and  selenium 
could  be  obtained  by  passing  the  hj^^’drides,  phosphine,  arsine, 
stibine,  etc.  into  aromatic  arsine -dichlorides , or  aromatic  ar- 
sine oxides  (15).  Arsenostibene  compounds  of  the  type  X’AsrSbX" 
have  been  made  (16)  in  which  X may  be  either  organic  or  inorganic 
radicals,  by  the  reaction  of  antimony  trihalides,  phenylstibine- 
dichloride,  etc.  on  aromatic  arsines.  Similarly  such  c ompounds 
have  been  made  (17)  by  the  reaction  of  stibine  oxides  and  aro- 
matic arsines.  Corresponding  reactions  of  compounds  containing 
bismuth  (IS)  instead  of  antimony  vdth  aromatic  arsines  have 
yielded  arseno-bismutliene  compounds.  However,  no  compounds 
containing  the  linkage  -As;H-  have  been  reported.  Such  a com- 
poimd  v/ould  -be  interesting,  since  all  of  the  above-mentioned 
analogous  types  containing  phosphorus,  antimony,  etc.  are  of 
therapeutic  value. 


10 


ITT.  THEORETICAL 

Since  aniline  is  readily  acetylated  and,  benzoylated,  it  seemed 
possible  that  analogous  products  might  be  obtained  from  phenyl- 
arsine;  CgHgAsIICOCngj  CgH^AsHCOCglig;  or  that  possibly  tv/o 

acyl  radicals  might  attach  to  the  arsenic.  Attempts  to  prepare 
any  such  compounds  were  unsuccessful,  with  practically  no  reaction 
occurring  at  all,  and  that  only  inizolving  the  formation  of  a 
little  arsenobenzene  by  the  reducing  action  of  phenylarsine . 

Palmer’s  (1)  aldehyde  condensations  led  to  the  investigation 
of  possible  similar  reactions  with  a ketone  capable  of  enolizing, 
as  in  aceto-acetic  ester.  Of  course  a reaction  analogous  to 
the  Claisen  reaction  with  the  ester  group  is  possible.  Evidences 
of  water  splitting  out  as  an  intermediate  step  v/ere  observed, 
but  the  final  product  was  arsenobenzene. 

In  an  attempt  to  prepare  a compound  containing  the  linlcage 
-As:N“,  similar  to  compounds  containing  phosphorus,  antimony, 
bismuth,  etc.,  in  place  of  nitrogen,  the  following  reaction  w’as 
thought  to  be  a possibility: 

CgHgAsHg  t ON-CgH^-lUCH^)^  = CgH^As ;N-CgH^N( CH3)2  t HgO. 

No  such  compound  was  isolated,  only  arsenobenzene  and  complex 
oxidation-reduction  products  coming  from  the  reaction, 

A v/hite,  cr:/stalline  product  was  isolated  v/hich  analyzes 
closely  for  (^20^24*^5^2^*® 2*  dissolves  readily  in  v/ater,  the 

solution  gradually  becoming  pink  and  turning  blue  on  heating. 

It  cannot  be  recrystallized  from  water  or  extracted  from  it  with 
immiscible  solvents.  It  reacts  acid  in  aqueous  solution,  and 
on  titration,  using  phenolphthalein,  gave  a neutral  equivalent  of 

in  excess  10/^  NaOH.  and  the  solution 


Vi  % jur  ifeii  ij 

’’or  ' - ’^■^•vir-.n^,;. 


Ml 


. V 

wv  ■■■ 


f^V- 


IV 


. 


.wi,™!'  .Tra.',  :%F.vi'.T 


y ,*  ■'  i .**vvr:  • •■  ' / I «;  1 * -'  ’n 

(d  W'4»v  4-cvi...  viJISitcs: 

^ Jn  • » . I ' . \ • '.*>■•  tel 


i 


'V.r'V 


4i. 

jjff'  < '.„:  ^ ^ I'J  , i- 


*-•  ifcuX  • •.'i-’h'-''*  .'<1  .'isiAX^* 


^!» 


'^f/' 


I • U.  ■ r-.-jJ.  , *‘  ..  ^c.’lj  *«^y’»fc:«'/(v  V-’*.#  . ■'■•ilf'ivj-  : 

fn-  ’i*  : ' • rTtii  ■ -J.  -.  T f ( Q J*’'‘^ 


» ' 


;,;  , filUw  . ;'.^^fyf^)f•:lll^^'*’  -'1' 

"' ^‘  :#n«  ” . ,. ; 'irr.;  ^ fti^;m.;*a 

-*  _!...■  ‘ ' sC»V 


S;  : ' 


* y.^t^v  • ■■  -v.;;  fi  :<c>  r '•v^, 


■j  uC^.  •»  .v\ 


ri<5viV>^^  ■•'ly/  i , — 1 

o#»,v  -1  Xr:i  apj^j  '^ol  »-C'Jfj 


/«  ' ' ' ■ '• 

wiWKr>:^C'  ^ " 

: ',r  V -•4A/-,,V..' 


**■*.'  *'  ^ • * ,‘,  . , ^ , , '.i 


: 'iiUje'i  'W  ^ .f 
, i;  f‘:.>  -‘^jUrji;  ■*  *tn" 


'fVl  X ■ ,V 


m < 


. v/„t .- .' vif* m.'  .-* •' i ^’  ’ 


■A  ; ‘ 


■.  ■ U ....a;.!'  ~ii.r  m?&;.,>5  rtS:  at.yttJlff ^ j ;, 


11 

is  colorless.  On  acidifying  in  presence  of  litmus  paper  the 
solution  tiorns  rose  pink  at  the  neutral  point,  hut  becomes  color- 
less in  very  slight  excess  of  acid.  Magnesia  mixture  v;as  added; 
no  precipitate  appeared  until  heating,  indicating  the  presence 
of  phenylarsonic  acid  (3).  These  observations  lead  to  the  con- 
clusion that  the  compound  probably  consists  of  an  amino  salt  of 
phenylarsonic  acid  and  some  amphoteric  substance.  It  seems 
possible  'and  logical  to  assume  that  the  nitroso  group  v/as  reduced 
to  a hydroxylamine  group  by  phenylar sine , and  that  water  split 
out  from  this  hydroxyl  group  and  a hydrogen  on  phenylars ine ; 

2 (CH3)2N-CgH4  -NO  t 2 CgH^AsHg  s 2 ( CH^) gN-CgH^NHOH 

^ CgHgA s 1 A s CgHg . ! 

(CH3)2N-CgH4NH0H  t CgHgAsH2  = ( CH3)2N-CgH4NH-AsHCgH5  t HgO  | 

air 

(CH3)2N-CgH4-NH-AsH-CgH5  Og  « ( CH3) gN-CgH^-NH-AsOOH-CgHg  I 

The  latter  compound  is  p- dimethyl amino  anilide  of  phenylarsonic  I 
acid.  Phenylarsonic  acid  (formed  along  with  arsenobenzene  by  the  i 
oxidizing  action  of  the  nitroso  group)  may  form  a salt  with  the 
dimethylamino  group  giving  the  compound, 

CgH5As0{0H)0NH(CH3)2-CgH4NH-As0(0H)GgHg.  | 

The  anilide  compound,  being  amphoteric,  would  be  soluble  in  both 
acid  and  alkali,  and  because  of  the  amphoteric  nature , a neutral 
equivalent  determination  would  not  be  of  any  value.  The  air 
oxidation  of  the  arsenic  coupled  to  the  nitrogen  wouild  explain 
why  considerable  length  of  tlm.e  (12  hours)  was  required  ..before 
the  material  appeared  in  the  acetone  or  benzene  solution  after 
the  reaction  had  gone  to  completion.  After  filtering  and  v^ithout 
concentrating,  frequently  a second  crop  of  crystals  would  be 
obtained  on  standing.  This  compound,  being  a salt  of  a very  weak 

— - ■ rT-'-—  ■'  - ..1  -U.A-  > 


at’-:"’'  r'*rr»B^  • 


y •.  rm.i-'i 


?g.:^i*8sw>rg>r:  AasgescjrHi^a-argrJi  * 


S’ 


'^r‘Lfv'  j T J I-  ^ I IjX  o 


'M 

• miiW  ' -i-  ' . "'1  jf  ^ H= 

...  .rv  ':.  -i  . .i... ..  1. 


■I  ..A 


V: 


* '.  .'* ' * > .‘i’.,  • ' i . ' ■ ■'* V .A^  '* 

'0| ,l«  v^i . k - V <6* »>  tv  >.  % il  ^ - -'* 

^ -.3^ 


,( . .y  fktJff^i^  '■>''■(  ■ ' 'fj  •tj.j 


^ < . *^#4^  '-•  - 


.’0»i 


X-  O' 


« ■ ■ »i'-f  ■•  ■^'  'tiiVj;  *■'  sii 


<v 

/■  '• 


e-' 


tir' 


- j?.. ;tv 


J n.* 


/ '^1 
3 ■ / t « 


/ • ^ 


iV 


,rsC->:>-'-:-,.^:-  V\,v  *%v- 

I 't  ■ ' ' '■■ 


,]/■' 


» fc,-.‘*fc-  • 


k *:ti  ; .Ufti;  v,  -;*  ^ ■ ’ ■ ("<:»K'»rn^c>’:j<^^tJI;^iX 

r'‘  ■ M!}  w 


. .ri'.'l/.tvpe. 


jxJt. ' i MX'  i vi  ' • > W \ 

Mj  ._ . ' ■ ’ , ;,V'\  * ••  | 


1 p^ 


- ...  - -^  ' V ' , , ‘J  -. 

t ."7*  ^ .5^  ’ 'f-i  . ^ 

^ ■ Mr'  '■  ^ '.'  ' '? 


•‘  . ••  j.  -j.  r'w.jjt  -JX:) 

.^»ip  ' A -., ^ - ■'■’«  \ ■'*/  >'  ' ,;4  ...:.5s 

^jgi.'-' ...4  v?cf  '* 

'VI-  ' t'  i;!^’.  W ’ ■ Vi  ".  ;^  ■'  ‘ . ‘ilil  ' ,Tii 


. ..♦ ' ;r/'»: 


’&»■'  4,L.; 


->r-  ’■  yi  V v.< J^T.  •^jM- 


ts'i  . x./(0‘.r  JiX 


. !■ 


t . ' ->  i'"«n  ' . .V' 


-'l^:^k.  Jf4; :;  r^vi* 

lA ■■a... , 


ts: 


.Wfin 


I 


12 

base  and  a weak  acid,  Vi^  on  Id  be  almost  completely  hydrolyzed  in 
aqueous  solution,  and  the  amphoteric  nature  of  the  anilide  com- 
pound would  interfere  with  its  extraction  w ith  immiscible  solvents 
as  was  observed.  The  para-diamino  structure,  being  s omev/hat 
unstable  and  subject  to  oxidation,  may  account  for  its  decomposition 
with  heat  and  its  color  play  v/ ith  ferric  chloride  and  silver  ni- 
trate . 

iiuch  of  this  assumption  can  be  substantiated  if  phenylarsine 
can  be  shown  to  c ondense  with  hydroxylamine s directly.  This  j 

investigation  will  be  taken  up  at  a later  date.  I 

A.  J.  <,iuick  found  in  this  laboratory  that  phenylarsine  re-  | 

acting  mth  two  mols  of  an  alkyl  Grignard  reagent  liberated  I 

quantitatively  two  mols  of  the  corresponding  hydrocarbon,  in 
accordance  with  the  follov;ing  equation;  I 

CgH5AsH2  t 2 RMgX  s GgH5As(MgX)2  t 2 RE  I 

This  phenylarsine -Grignard  complex  seemed  to  afford  a means  of  j 

attaching  various  halogenated  substances  to  the  arsenic  as  follows: 

CgH5As(MgX)2  t 2 RX  = C0H5ASR2  t 2 MgX2 
Or  it  might  be  possible  to  limit  the  reaction  to  the  formation  i 

of  s econdary  a rsines ; ! 

CgH5As(MgX)2  ^ RX  a CgH5AsR(MgX)  t MgX2 

CgH^AsR(MgX)  t HCl  = CgH^AsRH  MgXCl. 

The  application  of  this  method  to  the  formation  of  secondary 
arsines,  and  the  formation  of  tertiary  arsines  containing  three 
different  groups  has  not  yet  been  undertaken,  but  will  be  studied 
later.  ^'Nevertheless  it  was  found  that  in  certain  cases,  e.g. 
benzyl  chloride,  only  one  group  entered,  even  in  presence  of 


fHi^ft'i^P’XW'^'' "X  >tr^y^a  hlmr,  ,Mdo 

r e " '■  ■ *’  '■■  = 1 - • ) ‘ 0 ‘p7‘  ^ 

’ ,'4:.' /A.V  1 »•  .‘Vy:'^4, 

; K.  foij:  . -•  lix  .^l'.\; 


- -t  ■^.St\’:U 


i •■  ’^''  i^v*'  ^ ^1 


^ »)fii(nc'X'  fa/\i X V •■  i:"  if  x*i  i } Av^t.,  i ‘ 

^ '■  i . ';■  M ‘ ..  :f  , 

•^  \:\“'  V ^ * ' "‘’^■ 


i v.^*dL-  *5  .•  j t! , <j;  V *1(J?, 


■'’  df.  I f I V i 


^O'yt  :i  ■ i ‘#rv2ftv*{ci^yjf/vi-  '*.^.  V .^0 

^3  9 ‘-  iV  ' 1 . . V > ' '■■ 

. ' 'tir'  ■_  ) ■»!'  .‘  > 'M'  Aff^.f:  L’  ''iiii-Sfel'J^jii^Jv/^^ 


V ^v:/i:ii  j|jjl 

...4  * i . •*  - .'■*'/  '• ' '‘y||  ■.'• 

*■  » rr:'44>.  t. . . « *iC\¥.-»«c4.  ii' f* /Vli ’’  A.*  ♦ i If 

’ L«' 

i “ t=1  \ \ 

R ^ liri^'t.ffJiS)A''4kr!Mtt  ♦ ‘y  [r  4^)i$  ii?rx.fl;ji 


!r(Yi-.T.,,  ^ r art.? 

■ ^ \ sjM  '^'?  >■• 

■l'.g», : t a'/t;if).i  .'5«|,r  a r.'*',l -p^';T,.Rl^/ ,tPA 

«l  ; '&4’i,’  ■ 

; '.-oi;  al- ^ ' . J . ■ay?'  ;;/=  t'l^v. 

j ■ . ’ . t ' , ■ , i'A  :'  /'  y/flr,'  '.  , 

‘ .X*vL  ' 1 ■ ^ 

.;v  t « aetp,* 


f.WV->  SVf  .rtf'  6*i>ti ;?u-.-.  • o/ij^ VlbsWl^ 

III,  ,<  ■■^‘:'  ' 

r >w  1 : p ' • ..» t lo,.  • ^^i’STh^. 

l;  ^ '’  i’  '■  -'/■  ' •■.,  ;,{V...,,,.!^..  ..^i2'l''?i«p*''A  . ■ ^W'. 

wtj-  oi^v  :.'¥i  ‘ * ^ f ;'}^;  4^ 

■ , ‘>w  , ,:■  ' ,4..  f- ^ 

. .3  •••.?%<>«  *yf- -V#fX' 

.:  ^._  • . *;,.•'  •; :£•'  >mi»/'’<._..^.^'  ■ 1 1^- n.*'- ’• ." ••'/.'joi >i*^' a-  ' ■ ■ . 

■ _ y4.'..B:;  . '.,1  • •*  j'  ''/‘iT'Jb^B^  ' . |n'f:^ 


i^T.-:-  u-:i!ri 


13 


large  excess  of  benzyl  chloride,  presumably  on  account  of  steric 
hindrance. 

By  this  method  attempts  to  prepare  acetylated  and  benzoylated 
phenylarsine  by  the  use  of  acyl  clilorides  again  proved  futile. 
Tertiary  arsines,  hov/ever,  were  successfully  prepared  by  the  use 
of  ethyl,  propyl,  and  butyl  bromides  or  iodides. 

An  attempt  to  make  Palmer’s  (1)  benzaldehyde  condensation 
product  was  attended  by  no  reaction  at  all,  the  phenylarsine 
being  as^ain  liberated  on  adding  ice  and  dilute  HgSO^. 

Chloracetic  aster  did  not  couple  v/ith  the  phenylarsine -Grignard 
complex  as  one  might  expect  its  active  halogen  to  lead  it  to  do. 

On  the  other  hand  it  oxidized  the  phenylarsine  to  arsenobenzene , 
as  did  the  acetoacetic  ester  previously  mentioned,  presumably  at 
the  expense  of  the  carboxyl  group. 

Attempts  to  form  ring  structures  including  arsemic  by  the 
reaction  of  dihalo’genated  substances  on  the  phenylarsine -Grignard 
complex  all  were  unsuccessful.  The  preparation  of  a piperazine 
analogue  of  arsenic  seemed  possible  through  the  following  reaction: 


CeHsAs: 


J’i  X B:  hCHo-GHo-|Sr  XMg 

A A 

' Bil-CHo-CHo-iBr  ' xE 


^AsCgHg  = 


CgHgAs 


CHq-CHq. 

^..sCgHg  t 4 MgBrX 
CHg-CHg^ 


It  was  also  hoped  that  dichloroethyl  ether  might  yield  a morpholine 
analogue  as  follows: 


CgHgAs 


‘iS 


CiCHp-CHp 

> = C^HcAs^ 


CHg-CHg. 

CHo-CIL 


0 t 2 MgClX 


Likewise  pent ame thy lene  bromide  was  expected  to  yield  a piperidine 


THa*  ' Tw 

- •-*  , ir.  ' 


-H'  .t'i.i?  ' ^ .f'^CXiifo.U  rJir ^ 


f •, 


■i. . ■ ■ ■ . ## , 


’ ' ■•  6'.  • 

;'  ) 


: ..  * • < Vr  / 1 i.)  b;-. , . ■ *Hf  , '>  Y|.l-  4-' : V W ) 

■.'  ■;  IJ  .*..■«  'IT' 


u,. 


( -vv/' ' *VU’4i  '^1^^-, ‘ I' ‘'i-'.f ' 'iT'jjK- : J I 


‘ 


r* 


'»'r* 

Ml  W' 


■^•V  «s 


I ^ •.' ^i,*.  ' r eCStfi  * J'p.i 

I * '.  ’ . ' ' . \ * t ' I ' ^ 

' ,;53^4^  i>  '*  ^ ^ ^ y,  ^ . :^\t^  i. SI  -^)\y\‘"‘  , '-j  .f,  \V'fJ 

i ^ • Y X,.  ’ . - . - ■•!,*’  ''  » ‘ 


• “ ifc  7 ViSil  ■ ‘•‘ 

gi  i I • -^rntMi  -;.  t ' ;■  • ••  Vtv  ."  -•  ■•'^'h/'/m-’  »U  ^*k»  ,3.- 

H.  - ‘ 'M  . 


. ■' ' rri  '■  -!7 1 U'T.»4  ;k  >"■/!♦  V 


;'^  ^ ' ■ ■■':|.  I. 

t^y  • - V' X‘;  tn:  y~uUtrCn(^'.ln  LoJjii  f;'f’;Q^'  *•.  ,,c 

7 ■':•  ■''V.-’'i!ii:r' 


r 


X 


, a '-ft  «?vi,  r‘:iy 

’'iJ^-'  ^’.fj  ’ ' * 'uffl”  '■"' 

u “ I . n"  i "(I  it  I-  ^ ? M" •' * '' '•■' 

‘ ' * • * I.  {»  . 


-1* 


>'['Ji*j':'  M 

,!  ' itr 


X 


■ 


, b'/U  A c‘4:5»f' 


A t, ' ^ JCrt^X .'  ' t.  i'  -i  Y 

^ i .-/Ei  ' Mr  ■ jji  .-.'^r  ‘ 


i^-  ‘ 


t yf''"  “ 2 


V.W^| 


rX 


-oKO* 


f. 

I r'^" 


.'^  ■ -^  r,  ir 





.A 


■»..  e 

j 


;•  i,  'MnC  *■  S,': 


■J^;r.  !?':nrc;-»»'sf -<t^  i 


■;fl|«*3uaEr.-?: 


14 


analogue,  arsepedine  (20)  by  the  reaction, 

B ICHo-CHo.^ 


1 X 


CeHgAs 


* B:  hHn-CHo^ 


CHg-CHg 

CHg  r CgHgAs^  ^ MgBrX. 


’CHo-CH. 


No  substitution  was  found  with  the  ethylene  bromide  and  dichloro- 
ethyl  ether,  only  arsenobenzene  appearing  in  the  reaction  mixture, 
probably  from  the  behavior  of  the  Grignard  complex  as  an  alkaline 
condensing  agent.  Principally  arsenobenzene  resulted  from 
the  reaction  with  pent ame thy lene  bromide,  but  another  soluble 
fraction  V/ as  distilled,  and  the  distillate  on  standing  yielded 
crystals  of  phenyl  brompent ame thy lene  arsinic  acid. 


BrCH2CH2CH2CH2CIi2 


'AsO(OH) 


which  indicated  that  a secondary  arsine  had  been  formed,  phenyl 
brorapentarne  thy  lene  arsine. 


ErCHgC  HgCIIgCH  ^ Hg- 


AsH. 


Tith  benzyl  chloride  in  the  theoretical  amount  (2  mols)  only 
one  seemed  to  enter,  as  evidenced  by  the  subsequent  air  oxidation 
to  phenylbenzyl  arsinic  acid.  \"/ith  twice  the  theoretical  amount, 
however,  some  tertiary  arsine  probably  formed,  but  combined  with 
more  benzyl  chloride  to  yield  phenyl  tribenzylarsonium  chloride. 

No  coupling  could  be  induced  with  aromatic  halogens,  even  the 
active  halogen  in  p-chloronit robenzene . 

It  v;as  foimd  impossible  to  make  the  p he nylar sine -Grignard 
complex  by  the  action  of  magnesium  on  phenylarsine  dichloride, 
v;hich  might  be  expected  to  take  place  as  follov\Ts: 

CgKgAsClg  t 2 Mg  = CQH5As(MgCl)2^ 


a la.’l 


-«V' 


>\it  ' ::  ..'->^  * 

J;ir  '•  ■ • 


>".  . 1 ^ li 


?p 


r 


iV^ 

m. 

r i?  ^ . 

, o{  '. '' V /cr;  oC.-  , 

-v^:  . • h‘  . '.i  ..M  ..„r’  ■' 


fV.  ',«< 


liUv^  S.  iff  I W % :' 


ti"' 


f ^ '*h  syi-. 


. t/4 •*? . ^ 


S i * 


? -1  r^'.t:  ;c 

. ■ ^ 

A\ 


91 3 

-^■'  - , ■>  dV'fJr  / C ' ,v\K'  ' 

. :v 'kirMh^iKf  - ■-flh^  >6*'#X-wW2*fo 

vS^  ;'^:k 

(t-  < ^ 


t 


■ ■'*'’  • . • '■  ‘ ' ' \ i"’  i J4'i/'.!-i  ' 

';  ;■  I'i  ^*"11!)! 


.1 


’i^f',,  "Sil 


^9iy*  '?'.  *.*'** -^  -f  / i 

.vV«-  I.  ' ..  1 ' .V  i -ii,  '■;'.  « . 'Ll.  '.  Jj  . 

ACr  r:  • ..  r'&v fe'^jh'  <..  / 

» .» 


^'•*  •■  ■.V'fc’'  vij  t‘?i4ifii  ’'I-'.’  ^ A 


i^,'*Jl  .'  t.  J » ’JA.**  n;  j> 


.yt:v.-,  I ,)SS 

, ,j  -^r  •■'  ;•  •■  -'■*-  « 

, i a-'  'A..  V 


0 


b;  . ..■  ' •>  ^ ^ ^ 

, . /jii}4fc.i^  't  finJtau 


,.t 


><*•  ■ ■ ■■•>,.  V «s  ^\:b  '•i*,--.  1: 


n**  <•  * . i,  ,^.p  -If/  ’«f;  _{>:? 

1 .Jv)aVfr.  ^ qjV 

..  .n'"^'  ',^’ft  ^;^2>7-..!  s<  T '‘iP^SpX'j  '^i;-»,v>^  ^ 

•vv  ^ 

. '.■'*>'’■  ■.)  ’'i  , . ,.  ■ i '■  . . . ■ ■ 


AiV»TW3flir*rt 


f 4 


• ■/ 'j 


15 


Thus  it  is  seen  that  phenylarsine  shows  a very  strong  ten- 
dency to  act  as  a reducing  agent  on  oxygenated  substances  (even 
carboxyl  groups)^  and  dihalogenat eu  substances,  itself  being  ox 
idized  principally  to  arse  nobenzene . Consequently  reactions 
which  iruj^ht  be  predicted  by  analogy  to  reactions  of  the  amines, 
in  the  case  of  phenylarsine  very  frequently  occur  instead  as 
oxidation-reduct  ion  reactions  Vvhenever  the  opportunity  presents 
itse If. 


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16 

IV.  EXPElRIJffiNTAL 
A.  Preparation  of  Phenylarsine . 

Phenylarsonic  acid,  from  v/hich  phenylar sine  was  t o be  prepared 
by  reduction  was  made  by  the  method  desdribed  by  Norris  (7). 

For  this  purpose  tv;o  deep  cylindrical  copper  cans,  each  holding 
25  liters,  v/ere  used.  In  each  can  v/ as  mixed  one  kilo  of  arsenic 
trioxide  and  two  kilos  of  sodium  carbonate  to  which  v/as  added 
six  liters  of  v/ater.  Live  steam,  was  conducted  into  the  mixture 
v:ith  stirring  for  about  15  minutes  when  practically  all  the  ar- 
senic had  gone  into  solution.  This  step  v/as  found  materially  to 
Increase  the  yield,  as  the  arsenic  trioside  does  not  enter  very 
readily  into  solution  in  sodium  carbonate  at  ordinary  temperature, 
and  b e ing  heavy  is  likely  to  settle  into  a compact  mass  in  the 
bottom  during  the  diazot ization  even  though  stirring  is  employed. 
Then  45  gram.s  of  copper  sulfate  dissolved  in  water  was  added  and 
stirred  in.  The  tv;o  cans  were  placed  side  by  side  in  a deep 
wooden  tub  and  surrounded  by  w"ater  to  which  was  added  a little  ice 
occasionally  as  needed  to  maintain  the  reaction  mixture  at  15°. 

For  each  of  the  twn  batches  four  charges  of  diazo  solution  were 
made  up  as  needed,  each  charge  containing 
186  grams  {182  cc.)  aniline 
400  cc . concentrated  HCl 

1 liter  water  and  ice  to  make  up  5 liters. 

140  grams  NaN02» 

For  the  diaao  sollition  two  large  bottles  v;ith  side  vents  at 
the  bottom  were  used  from  which  the  s-olution  was  donducted  by 
a tube  provided  with  an  adjustable  pinch-cock.  The  aniline  and. 


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17 


water  were  put  in  these  bottles,  and  to  it  v;as  added  the  HCl. 

Ice  was  added  to  make  up  to  three  liters  (previously  marked  on 
the  bottle),  and  the  sodium  nitrite  dissolved  in  as  little  v/ater 
as  possibly  was  added  s lov/ly  with  stirring.  The  sodium  arsenite 
solution  v/as  efficiently,  though  not  vigorously,  stirred  with 
motor  driven  stirrers,  and  the  diazo  solution  was  ru.n  in  slowly 
in  a stream  about  the  size  of  the  lead  in  a pencil.  At  this 
rate  the  ice  is  sufficient  to  keep  the  solution  cold  until  it 
is  all  run  in.  Considerable  frothing  occuirs  because  of  the 
evolution  of  carbon  dioxide,  but  the  occasional  addition  of  a 
little  benzene  is  effective  in  contbrolling  it. 

The  m.ixtujT-e  is  stirred  for  an  hour  after  all  the  diazo 
solution  has  been  run  in,  and  then  allowed  to  stand  over  night 
in  order  to  allow  tarry  matter  to  settle  out.  After  filtering, 
the  solution  is  concentrated  in  large  evaporating  dished  on 
steam  cones  to  about  five  liters  for  each  batch.  At  this  point 
the  addition  of  100--200  cc . of  concentrated  HCl  ¥/ill  precipitate 
considerable  tarry  matter  withoiit  throwing  dov/n  any  of  the  acid. 
It  should  then  b e filtered  and  cooled.  The  combined  batches 
(about  10  liters)  Vi/ere  put  in  a four  gallon  stone  Jar  Vi/hich  was 
set  in  a sink  and  cooled  v;ith  running  v/ater.  Concentrated  HCl 
v;as  added  with  stirring  until  the  reaction  to  litmus  paper  was 
decidedly  and  promptly  acid.  The  phenylarsonic  acid  separated 
out  until  the  contents  of  the  Jar  were  almost  solid.  After 
standing  over  night  the  acid  v/as  filtered  and  sucked  dry  as 
possible  and  washed  with  a little  distilled  Virater.  The  nearly 
white  product  Vvas  spread  out  to  dry.  The  filtrate  was  neutra- 
lized vjith  ammonia,  and  a solution  of  ferric  chloride  added  as 


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18 


precipitation  continued.,  it  being  necessary  to  add  more  ammonia 
from,  t ime  to  time  to  maintain  a neutral  solution.  The  ferric 
salt  formed  is  very  insoluble  (the  filtrate  gave  no  reaction  v;  ith 
potassium  ferrocyanide ) ; it  is  v;hite  and  very  fine,  settling 
slowly  and  filtering  with  difficiilty.  This  product  is  of  course 
very’'  impure  since  tv/enty  per  cent  excess  AsgO^  v;as  used  at  the 
start  and  v/illbe  precipitated  as  ferric  arsenite.  Neverthe- 
less it  serves  equally  as  v;ell  for  rediiction  as  the  free  acid. 

Its  content  of  phenylarsonic  acid  depends  of  course  on  the  com- 
pleteness of  the  precipitation  of  the  free  acid,  v;hich  varies , 
Thirty  per  cent  yields  of  phenylarsine  were  obtained  from  the 
iron  salt,  vi/hereas  the  yields  on  the  free  acid  average  betv/een 
forty  and  sixty  percent,  A yield  of  93  percent  phenylarsonic 
acid  based  on  the  aniline  was  obtained  by  this  method. 

For  the  preparation  of  phenyrlarsine  the  pheny^lar s onic  acid 
was  reduced  with  amalgamated  zinc  dust  and  hydrochloric  acid: 
CgH^AsO^Hg  t 6 H = CgHgAsHg  t 3 HgO 

Batches  of  200  grams  (1  mol)  v/ere  reduced  using  400  grams  zinc 
dust  (6  m.ols,  or  twice  the  theoretical  amount)  and  one  liter  of 
concentrated  HCl.  About  25  grams  of  mercuric  chloride  v/as 
dissolved  in  a liter  of  water  in  a 5 liter  round -bottom  IPlask. 

The  zinc  dust  was  added  and  shal?:en  up  several  minutes  to  insure 
even  amalgamation.  The  phenylarsonic  acid  v/as  then  ad.ded  and 
the  v/hole  mixture  v/ell  shaken.  The  flask  v;as  fitted  with  a two- 
hole  rubber  stopper,  one  hole  for  the  condenser,  and  the  other 
(v/hich  is  plugged  during  the  reduction)  for  a delivery  tube  to 
draw  off  the  ether  layer  after  reduction.  In  the  top  of  the 
condenser  was  fitted  a 500  cc.  dropping  funnel  and  a vent  tube  for 


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19 


the  escaping  hydrogen  TCJhich  dipped  into  a test  tube  containing 
ir.ercury  to  serve  as  a trap  to  prevent  entrance  of  air  into  the 
apparatus.  A half  liter  of  ether  v;as  admitted  through  the 
dropping  funnel  and  was  replenished  occasionally  as  it  v;as  car- 
ried out  with  the  escaping  hydrogen.  The  apparatus  was  placed 
in  a sink  and  the  condenser  v/ater  allowed  to  run  dovm  over  the 
flask  in  order  to  minimize  the  loss  of  ether.  The  hydrochloric 
acid  was  admitted  slowly  through  the  dropping  funnel  in  batches 
of  250  cc . per  day  and  the  m.ixture  allowed  to  stand  a day  or 
two  after  all  the  acid  had  been  added.  If  the  process  is  hurried 
a considerable  amount  of  zinc  is  1^'ft  unattacked  in  the  flask  and 
a low  yield  of  phenylarsine  is  obtained. 

The  plug  is  rem.oved  from  the  stopper  in  the  flask  and  the 
delivery  tube  inserted  Vvhich  runs  into  a liter  separatory  funnel 
supported  on  a ring  stand  from  the  floor.  Ftised  calcium  chloride 
is  placed  in  the  funnel  and  COg  conducted  into  it.  It  was  found 
that  placing  a v;  ad  of  glass  wool  in  the  bottom  of  the  funnel 
prevented  much  annoyance  from  the  stop-cock  sticking.  Water 
v;as  admitted  through  the  dropping  funnel  until  the  ether  layer 
arose  and  was  forced  out  through  the  delivery  tube  into  the  se- 
paratory funnel,  v;hich  w’as  then  stoppered  and  allov;ed  to  stand  for 
about  an  hour.  The  dried  ether  solut ion  vi?as  then  run  into  a 

distilling  apparatus  consisting  of  a 500  cc . distilling  flask 
and  a 250  cc.  receiver  from  vi/hich  the  air  had  been  displaced  by 
COg.  A small  tube  extending  to  the  bottom  of  the  distilling 
flask  conducting  dry  COg,  its  flow  being  regulated  by  an  ad- 
justable pinch- cock,  v;as  used  to  prevent  bumping  and  oxidation 
during  distillation.  The  ether  was  evaporated  off  over  a steam 


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20 

jet  and  allowed  to  pass  on  through  the  uncooled  condenser.  An 

aspirator  was  connected  (with  a three-way  stop-cock  and  a manometer 

in  the  train)  to  the  condenser  and  e vacuat ion  started,  restricting 
» 

the  flow  of  CO2  hy  the  pinch-cock  so  that  its  rate  of  bubbling 
through  the  drying  tube  was  somiewhat  less  than  before,  insuring 
no  admission  of  air  into  the  train  betv/een  the  flask  and  the  CO2 
tank.  ?/hen  the  phenylarsine  began  to  distil,  the  condenser 
was  cooled  v;ith  running  water.  After  completion  of  the  distil- 
lation, the  three-way  stop-cock  in  the  aspirator  train  was  closed 
and  COg  rapidly  admitted  to  fill  the  apparatus.  For  preserving 
the  phenylarsine  test  tubes  were  draw^n  out  to  a narrow  neck, 
filled  with  CO2J  stoppered,  labelled,  weighed,  and  the  weight 
marked  on  the  label.  The  receiver  v/as  removed  and  immediately 
stoppered  v/ith  a rubber  stopper  lihrough  which  passed  a small  tube 
conducting  ^^02  • The  phenylarsine  was  then  carefully  poured 
out  through  the  sidearm  of  the  receiver  into  the  test  tiibes 
which  were  then  immediately  stoppered.  The  steady  stream,  of 
CO2  prevents  any  oxidation  whatsoever.  The  tubes  were  sealed 
off  at  the  neck  and  Vveighed,  each  with  its  corresponding  stopper 
and  sealed-off  piece.  This  weight  is  entered  on  the  label,  and 
by  difference  is  obtained  the  v/eight  of  the  phenylarsine  in  each 
tube.  This  method  is  much  more  satisfactory  than  attempting  to 
weigh  up  a sample  for  each  experiment.  Portions  of  15 — 20  grams 
were  pit  up  in  each  tube.  The  capillary  tip  can  be  snapped 
off  the  tube  and  its  contents  transferred  to  a reaction  apparatus 
with  practically  no  loss  from  oxidation. 


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21 

B.  Reactions  with  Phenylars ine . 

With  Acetic  Anhydride , 

Phenylars ine  (17  g)  was  added  to  3 mols  of  acetic  anhydride 
in  an  atmosphere  of  CO2.  No  discernible  evolntidn  of  heat  nor 
evidence  of  any  reaction  was  observed.  The  mixture  v/as  refluxed 
over  night  and  vacuum  distilled,  all  passing  over  in  the  neighbor- 
hodd  of  85°  at  50  mm.  pressure,  Phenylarsine  boild  at  84°  at 
55  mm.  The  effect  of  a few  drops  of  Concentrated  H2S04was  tried: 
it  sputtered  as  it  was  added  but  no  change  was  observed  except 
the  remainder  of  a small  am.ount  of  tarry  matter  on  distillation. 

With  Acetyl  Chloride^ 

Three  mols  of  acetyl  chloride  were  added  to  the  distillate 
containing  the  phenylarsine  and  acetic  anhydride  and  refluxed 
several  hours.  No  solid  product  appeared.  On  distillation 
considerable  dark  tarry  substance  remained  in  the  flask  under 
90°  at  45  mm.  On  attempting  to  take  up  this  material  in  benzene 
the  m.ass  loosened  up  and  partially  went  into  solution.  The 
part  insoluble  in  benzene  v/as  taken  up  in  alcohol,  decolorized 
v/ith  bone-black,  and  evaporated  in  an  attempt  to  crystallize, 
but  practically  nothing  remained.  Apparently  the  material, 
which  v/as  very  dark  brov/n,  remiained  with  the  bone-black. 

The  reddish-brov/n  benzene  solution  was  evaporated  on  a steam 
bath  to  dryness,  leaving  a sticky  transparent  residue;  this  was 
taken  up  in  alcohol  and  decolorized  with  bone-black.  On  con- 
centrating, a little  sticky,  transparent,  pale  yellov/  residue 
was  left  which  v/as  recrystallized  from  benzene  and  identified  by 
mixed  mielting  point  as  arsenobenzene , It  seems  likely  that  a 
little  phenylarsine  remained  with  the  tar  and  oxidized  on  expo- 


'V* 


I 


[»  » . 


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9 


•>«  ..  /•,  -aj  ■ •;,.. ,' 


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. , ".  ‘ ■'  f . . ■*.'  •:  • ’«  I.'-*-  !'  ' W •jJiv'i^' 

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vsci'scs^r^ft*  cs«^i; 


22 


sure  to  the  air  to  arsenobenzene . Apparently  no  clearly  defined 
reaction  occurred. 

With  Benzoyl  Chloride , 

Phenylarsine  (16  g)  was  sealed  up  v/lth  three  mols  of  benzoyl 
chloride  and  a small  excess  of  CaO  in  a bomb  tube.  No  heat  was 
evolved,  and  no  change  was  apparent  after  several  hours.  The 
tube  was  left  in  a steam  bath  over  night;  the  contents  turned  red 
and  on  cooling  solidified.  Considerable  pressure  was  evident  on 
opening  the  tube.  The  mass  was  extracted  tvirice  with  ether  and 
the  residue  treated  with  hot  benzene. 

The  ether  extract  was  shaken  out  6 --8  times  with  dilute  NaOH 
to  rem.ove  benzoic  acid  and  benzoyl  chloride.  The  ether  was 
evaporated  off,  leaving  a pale  yellov;  oil  which  solidified  on 
exposure  to  the  air  for  a short  time.  It  would  not  then 
redissolve  in  ether.  Before  solidifying  phenylarsine  was 
apparent  from  its  odor  and  blistering  action  on  the  skin.  The 
solid  was  purified  and  identified  as  arsenobenzene  by  mdxed  mel- 
ting point.  Arsenobenzene  was  also  found  in  the  benzene  extract 
from  the  original  product.  No  evidence  of  a benzoylated  phenyl- 
arsine was  found. 

With  Acetoacetic  Ester. 

Phenylarsine  (6.8  g)  with  two  mols  of  acetoacetic  ester  and 
three  drops  of  concentrated  HCl  were  sealed  up  in  a bomb  tube. 

There  was  no  noticeable  evolution  of  heat,  but  the  mixture  became 
immediately  tiu’bid  and  colorless  globules  gradually  separated 
and  rose  to  the  surface  forming  a layer  corresponding  approximately 
to  the  theoretical  volume  of  water  splitting  out  mol  for  mol  v/ith 
the  phejiylars ine . This  layer  gradually  disappeared,  and  the 


-.TMjLp.r 


5;'’-  ‘ .‘-M  T4,  7 (?:  14,.^ 


} :■'■•"•  ■ "■ii 


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23 

mixture  turned  slightly  yerllow.  After  warming  gently  for  a fev; 
hours  and  cooling,  a very  small  amount  of  crystalline  material 
appeared.  It  was  heated  over  night  on  a steam  bath,  v/hereon  a 
mass  of  large,  nearly  white  needles  had  formed  to  a depth  of 
about  one -fourth  of  the  liquid.  On  continued  heating  the  mdxture 
became  a solid  mass  of  crystals,  and  a little  liquid  condensed 
on  cooling  the  tube.  Very  high  pressure  viras  observed  on  opening 
the  tube.  The  released  gas  had  a pleasant  ester-like  odor. 

The  crystalline  solid  v/as  found  to  be  almost  pure  arsenobenzene . 

On  recrystallization  from  benzene  it  showed  no  depression  in  a 
mixed  melting  point  v/ith  pure  arsenobenzene, 

VJith  p-Nitrosodimethylaniline . 

Phenylarsine  (16.6  g)  dissolved  in  dry  petroleum  ether  was 
slowly  admitted  to  one  mol  of  p-nitrosodimethylaniline  in  petro- 
leum ether.  Since  the  amine  is  spai'ingly  soluble  in  the  ether, 
the  m.ixture  was  shaken  during  the  reaction,  which  proceeded 
vigorously,  but  was  subdued  on  cooling  v;ith  ice.  After  the 
reaction  a black  tar-like  material  insoluble  in  the  ether  remained; 
it  was  washed  with  petroleum  ether  and  treated  w ith  b enzene , in 
which  it  was  largely  soluble.  The  residue  was  found  to  be  sol- 
uble in  alcohol  and  v/ater,  imparting  to  each  a deep  blue  color. 

The  deep  red,  almost  opaque  benzene  solution  v/as  found  to  contain 
a small  amount  of  the  unused  p-nitrosodimethylaniline;  on  con- 
centration several  crops  of  brown  soft  crystalline  material  were 
obtained,  which  were  evidently  contamdnated  by  the  blue  substance. 
It  v/as  found  practically  impossible  to  separate  the  blue  material 
from  the  rest.  Even  the  first  few  crops  of  cryttals,  v/hich  v/ere 
nearly  free  from  it,  after  several  recrystallizations  from  chloro- 


’•’K  i?nv> 


tJH  .,.  ..'1.'  J 


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1 


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24 


form  showed  traces  of  it. 

For  this  reason  the  entire  reaction  was  repeated  in  benzene 
in  vi/hich  the  amine  v;as  first  completely  dissolved.  In  this  case 
no  blue  substance  v;as  formed,  and  no  odor  of  phenylarsine  v/as 
evident  after  the  reaction.  The  solution  as  before  v/as  deep 
red.  On  concentrating  and  after  standing  about  12  hours  the 
material  crystallized  out  as  in  the  first  case,  and  was  recrystal- 
lized from  chloroform:  m.p,  140°  (darkens  between  130°  and  155^) . 

The  reaction  was  similarly  carried  out  in  acetone  v/ith  much 
the  same  results,  except  that  a cleaner  product,  and  a somewhat 
better  yield  was  obtained  directly  on  concentration  of  the  re- 
action mixtur-e;  6,8  grams  of  unre crystallized,  nearly  white 
product  was  obtained  from  14  grams  of  phenylarsine.  IfJhen  the 
acetone  solution  was  concentrated  to  a very  small  volume,  a 
crop  of  crystals  v/as  obtained  rich  orange  in  color  and  insoluble 
in  water,  but  soluble  in  dilute  acid  to  a deep  red  color.  It 
was  consequently  -purified  by  dissolving  in  dilute  E2^0^,  filter- 
ing to  remove  arsenobenzene  (considerable  of  v/hichv/as  present), 
precipitating  with  dilute  ITaOH  solution,  and  filtering  with 
suction.  It  v/as  recrystallized  from  acetone : m.p.  266--267°. 

4,4  ’ -dime thy lamino -azobenzene , ( CH|^)2N-C0H^-N:N-CgH^N ( CH^) 2 
melts  at  265°  (Richter^.  The  remaining  acetone  solution  con- 
tained a black,  tarry  material, 

BecaxTse  of  the  formation  of  considerable  arsenobenzene  and 
azo  compound,  it  v/as  considered  that  the  oxidation  might  be  less- 
ened by  greater  dilution  v/ ith  acetone  and  by  running  the  nitroso 
compound  into  the  phenylarsine.  Consequently  the  phenylarsine 
(14.7  g)  v/as  dissolved  in  400  cc.  of  acetone  and  the  nitroso- 


— ..(  '•  ti  ’Tvr  '■■  '*Hj_^Sf^f'f  "'^'''■''!;^t^*■'‘^  ‘ ''  '’;v  3 

/■  rMij  ^ / ' V. '#.1  It  ' fl 


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25 


dlmethylaniline  (1  mol)  in  300  cc.  of  acetone  was  added  dropwise 
m'ith  stirring  caused  by  bubbling  COg  through  the  phenylarsine . 

The  deep  green  nitroso  solution  ;vas  decolorized  as  it  promptly 
reacted,  even  though  the  solution  v/as  cooled  with  ice,  until 
about  one-third  of  it  had  been  added,  then  the  reaction  mixture 
became  green.  After  standing  over  night  a sm.all  amount  of  cry- 
stalline material  had  appeared.  Four  crops  of  crystals  were 
obtained  by  successive  concentrations,  the  last  being  alrmst  to 
a syrup  and  requiring  much  washing  with  acetone  to  remove  the  tar. 
Hov/ever  none  of  the  p-di(  dine  thy  lamino)azobenzene  appeared  as 
in  the  previous  modification  at  this  stage.  The  yield  was 
also  somewhat  higher,  am.ounting  to  7.6  grams  of  crude  product. 
Even  better  yields  and  more  satisfactory  resu.lts  were  obtained  by 
adding  the  nitroso  solution  at  once  v/ith  vigorous  shaking  in  the 
cold. 

The  white  product  crystallized  from  chloroform  in  fine  white 
fluffy  needles.  It  v/as  almost  instantaneously  soluble  in  ¥\rater 
but  could  not  be  recovered  from  it  either  by  concentration  on  a 
steam  b ath  or  extracting  with  iiranlscible  solvents.  On  concen- 
tration it  turned  blue  and  on  coming  to  dryness  appeared  as  a 
dark  blue  residue,  probably  the  same  as  obtained  in  the  earlier 
reactions.  The  aqueous  solution  gave  vivid  color  reactions 
viTith  silver  nitrate  and  ferric  chloride  solutions. 

Subs.,  0.1487:  COg,  0.2512 

Calc,  for  Cg^Hg^O^NgAsg:  C,  46.00^.  Found  46,10^ 

Subs.,  0.1284:  18.27  cc.  Iodine,  1 cc . r 0.002  g.  As. 

Calc.:  As,  28.75^L  Found  28.44,^ 


i > 


A 


26 


Subs,,  0.3984:  19.7  cc . N at  28*^  and  740.5  mm. 

Calc.:  N,  5.37^.  Found  5.35^ 

The  arsenic  was  determined  by  Robertson’s  method  (19). 
Analyses  v/ere  made  on  pure  arsenobenzene  in  an  attempt  to  apply 
the  Parr  peroxide  bomb.  The  fusion  was  acidified  v;ith  HCl  and 
boiled  to  decompose  the  H2O2;  the  arsenic  was  precipitated  in 
strong  HCl  in  the  cold  as  the  pentasulfide  and  weighed  in  a Gooch 
crucible  (Treadvjell-Hall,  vol.  II,  p.  205)  . Good  results  were 
obtained,  but  the  method  proved  unsatisfactory  with  the  compound 
containing  nitrogen,  probably  because  of  the  formation  of  oxides 
of  nitrogen  in  the  fusion  and  the  subsequent  liberation  of  free 
sulphur  in  the  precipitation  v/ith  H2S.  Attempts  to  extract  the 
free  sulphur  v/ith  CS2  according  to  Treadwell-Hall,  vol.  II,  pp. 
169--170  were  unsuccessful  because  of  the  tight,  compact  nature 
of  the  precipitate. 

With  ^ Ketone  Gri.gnard  Compound. 

To  ethyl  magnesiixm  b romide  (2  mols)  lo/as  added  two  mols  of 
dry  acetone.  After  the  reaction  v;as  complete,  17.7  grams  of 
phenylarsine  (1  mol)  v/as  added.  No  reaction  was  apparent  and 
the  mixture  v/as  refluxed  with  stirring  for  several  hours.  Ice 
and  dilute  H2S0^  v;ere  added  and  the  ether  layer  separated.  The 
odor  of  phenylarsine  'was  apparent  in  the  ether,  and  considerable 
arsenobenzene  crystallized  out,  v>fhich  v/as  identified  by  mixed 
melting  point.  Evidently  no  reaction  took  place, 

C.  Reactions  with  Phenylars ine-Grignard  Complex. 

Phenylarsine  was  dissolved  in  anhydrous  ether  and  to  it  was 


I 


J L . 

. i i , i 

r , • 

• • C * i-’Wi 

■ »ri‘  , . 

* 

<X‘  -i.K.- 

• w» 

» 

•a 

y.  ^ r 

" ~ • r 

J.  .1 

r.,  ., 

- 1 •/'  >»: 

.'.  '7  : ■ • 

r."  ■ f .. 

* 

n.’  ' 

»>•  ■ 

'‘  i ■ . 

Xi  -r  i: 

■ ' ’ ■ • f ' 

:.!in 

! ' ' ‘.)p 

- 'tl  io 

‘ i.  -i  i *.v 

■ ■ :^.v  . ? ’J 

• 

• ■'  • - 'I  nf'il 

i' 

' ; 

i't>r  ''I'  ■• . ■ , 

:V,r ' 

' , t ' 

• . . V 

ic  r 

.....  ■ ]. 

- ■ ' U 

. ,*  . r , 

•■.»■■■■ 

! • - . 

. ■ . - i ' 

rr  ^ t 

4 

s 

f.  ' '-X-.  . , 

■■’  ■■  . • i fj,.- 

f 

- ’ . ■■'  ■ . ■ , - ► ■ ^ .iC  .. 

rr  i /, 

oj.  , 

i''  , ■ hi  : ./• 

; o 

I’j  < * ■•' 

' ' . . r,,  (:j  . ' 

‘ - f*  . • 

27 

slowly  added  two  raols  of  an  alkyl  magnesiiim  halide  in  e then 
(ethyl  bromide  was  used  for  making  the  Grignard  reagent;  methyl 
iodide  was  tried  but  trouble  v^as  encountered  from  iodine  being 
liberated  on  decomposing  the  Grignard  with  dilute  HgSO^j  which 
combines  readily  w/ith  substituted  arsines) . A voluminous  evo- 
lution of  gaseous  hydrocarbon  occurred,  and  the  reaction  mixture 
needed  to  b e cooled  ocasionally.  The  reaction  was  carried  out 
in  an  atmosphere  of  dry  nitrogen;  as  it  proceeded,  a layer  of 
heavy,  greenish  oil  separated  beneath  the  ether  layer.  An 
attempt  was  made  to  isolate  some  of  the  product;  the  ether  v;as 
distilled  off  under  vacuum  in  a water  bath  which  v; as  gradually 
raised  to  60°  where  it  was  maintained  for  over  an  hour.  Nitro- 
gen v/as  then  admitted  and  the  muss  cooled  dov/n;  it  remained 
soft  and  transparent  like  a heavy  syrup.  A portion  removed  on 
a glass  rod  oxidized  readily  in  the  air  and  smelled  strongly  of 
phenylarsine . Since  the  product  v;ould  not  crystallize,  no 
attempt  was  m.ade  to  analyze  it. 

T/ith  Acetyl  Chloride . 

Phenylarsine  (15  g)  v;as  converted  to  the  Grignard  complex 
and  to  it  v;as  added  two  mols  of  acetyl  chloride  dropv/ise;  the 
reaction  flask  v;as  surrounded  by  ice,  yet  the  reaction  was  ex- 
ceedingly violent  until  about  half  the  acetyl  chloride  had  been 
added.  At  this  point  a light  yellow  solid  began  to  separate. 

By  the  time  all  the  m.aterial  had  been  added  a heavy,  semi-solid, 
oil-like  material  separated  which  soon  solidified;  after  standing 
stoppered  for  an  hour  the  mass  v/as  nearly  solid  except  for  a little 
ether  yet  present.  The  odor  of  acetyl  chloride  was  still  strongly 
apparent . 


MM*  I—  ■ — 


I ywfci'w 


^•"  y'  VYm' 


■s’wl"i 


f ■"  iv..  flit  .\i:i'*3«ert  fc-tt,>9iSf-  .'fij 


’Si 


h&jj  (i  M‘  , ,.  (,:  ‘ic  ^ ciiKi  ^ai,Vt 


• I 


r-.  ?3.p  ‘ S'' . * '«.  t *.’4.<^’.  N'  \;ii 

f '-'  t,'  • ■ ' ” j >''.'»  ■‘'•■'V’ 


; • ■•.  .i,,  v,^/  -i  £#•».->),  , 


\/  #<^-r  ^ /‘v^7V  I,;  *>, ■'/Vi.  rv*. 


^ ‘,7'y 


1-tsk 


/•frr 


v4 


f»  ':'P? 


• '♦  V s-  »'  v^_»,  1^ 


I i < 


*i:  r -sti.io' 


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-^i  : i ]*•  f >7/ 


\n  > »:•' 


*-  >%, ? ■,  f #.n\ : *'  '*<r- ''■■IjiiiSo a 

. , , 1*  1 . • • ' i * - 


;.■  '*ii  •'■  % ' Tilsit  f I ?i..  tS/T  .fvl/j  \ -'itx.'fe t. 

■ '«v  ' Ji"  ’ > •'.  * >j 


^ ’-  r..-  . -w;g  ifi.' ^ i 

'j'  •>  * ••*7  ' - ''Ai^ ■ '"  ■/*'  V,  ' *w' 

ii-!®*’  - •'•-->■  ■ '.’  • -v:a  r-  ores  c.&.- 4,  ri  i;^<i,  » 

..  ,:. , v- . ::.’i^:  \ .. ..'  i.iJ 


..  . /f-'  ■ ■■  V-  ' :'>J ' 'hi  ’■  S'K 

tTfitTCt/i**/  . t/tj  -iffy 

. r'  .;^'  "11  ■•^  ' "''V 

-A.v<j  -nj'l  ..‘'•TV  T 

, ..  7'r^™  ’S,,  ‘ .-U  ' W-« 


-,  ^Trc  OovQr*<fi  Mot.:-xo,;„  jg.,  ,‘^.i£  Jbtp-xvrfWfj-'xi  Afti: 

* , '^  ■ ' ’^^t*  ' ” *7V-  !■  ” "ts  J"  ‘ ' R'”'' 

.^r;.  ^ r:4rTv/|JC|(l  ‘V^:’  ^ M 


,C'  I • 

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y 


i*^ 


. f ISjS  ilAi  P itO,  . 

v.  37  ;■'  ft  * 

• mm 

^ J ^ - I'lV 


r 4/’-  Ui  .’i-t/flp-4-;'  ->?>“. T'.y  .i,  :i<s|r  Cxi  ?^/y‘ 

. ; '■  crCB  oxcf  W 


- '1> . a*!'  / / ir\x  .1  p 5’'. *-t  i,h  T ‘ '■  . '^l  Y --^  rt/fT'x^w ' ' 

■ .)  .,1  ■■'<'•  ' “ ''  • 'fr-  ••'<’  /'  f >■  ■ _ ■■  -i-i 

- ' . i ' ' ,'_  ■.•  • ■ 

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f ‘>*:4  itjfcd  lj*i  j , w 

'?i:xX-IX9  i 


<f  * 


r in< C .'  ..  ,4  f 7'0(,  ‘ .' '' 

j 'I  i!  ^^1  Ai 


■'  ■'<  .1? 

/i.j  »'/,> 


*'k.,v!>r.'j 


c:=r:r. 


28 


Water  v/as  added  and  the  mixture  extracted  w ith  ether.  The 
solid  material  v^as  washed  with  water  to  remove  the  magnesiujn  salt, 
recrystallized  from  benzene  and  identified  as  arsenobenzene , 

The  ether  extract  v;as  vacuum  distilled,  but  v/as  exceedingly 
small,  only  about  2 cc.  of  distillate  being  obtained  boiling  at 
206°  at  44  mm.  with  partial  decomposition. 

With  Benzoyl  Chloride . 

The  prededing  experiment  was  duplicated  using  benzoyl  chloride 
in  place  of  acetyl  chloride.  Results  were  practically  the  same, 
though  the  reaction  was  not  nearly  so  vigorous.  The  reaction 
mixture  was  solid  by  the  time  all  the  material  had  been  added, 
and  was  orange  color.  The  solid  material  after  extracting  w ith 
v;ater  was  found  to  consist  mostly  of  arsenobenzene.  The  ether 
solution  yielded  a very  small  high  boiling  fraction  Vihich  on 
cooling  partially  solidified. 

With  Eth:~  1 Iodide  and  Bromide . 

Phenylarsine  (17  g)  was  converted  to  the  Grisnard  complex 
and  two  m.ols  of  ethyl  iodide  were  added  to  it.  A lively  reaction 
occurred  causing  the  ether  to  boil.  When  the  mixture  had  cooled, 
it  was  a homogeneous,  nearly  colorless  solution.  Ice  and  dilute 
H2S04  v/ere  added  to  the  mixture:  no  solid  appeared  and  no  odor 

of  phenylarsine  was  apparent.  The  ether  layer  was  separated 
and  the  aqueous  fraction  v;ashed  once  v/ith  ether,  v/hich  became 
dark  from  iodine  liberated  from  decomposing  HI,  This  color 
disappeared  on  c ombining  with  the  original  ether  fraction.  The 
ether  was  evaporated  under  vacuur.i  leaving  a colorless,  mobile 
liquid  which  distilled  with  considerable  decomposition  over  a 
wide  range,  220 --260°. 


f.  V T 1 


fVi 


-«-.’T5,a  '<■  w ^ , , . ^ 

44l^tsii  U-X<»?_‘V^  .%(:}  Jlfi  ;i  34J»f/  *i*‘J’iC!] 


'■  > 'v  'wj  ■/  ■ ".  . ■■'•  ' »;  . 

-:'r  r * li  X^lx»v  ■“'  " I 

; . vJi'Jdi'i.'  '!»i'  ■’  ' ' ! \fi-7jux«;  rtp^)  i4-^4.vi»^*{ao‘3: 

M"  • ••„»  ‘ift^  .r.  , * . 'H 


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^'y*V  v-i-’‘!w^'  ^■-  •?;*'<■.■  ' 

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.H  . I * ■.•.  ■*  * * *.' 


.ft 


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I ‘ •: . ftil  . ;{!A<kT<3.  v«'V  'W  .^jer; 

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Ijt^ivvv’'  ■/,,-*  , S '.  i : r H cr/  V'l' i^'I > 

..._v...-  .0  'i 


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' ft 


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: *<■-■  >•  tyffl  rj;/ 

' * ■ M f '*  t 

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HS' i '■  '■  ’-'*■■  • 

BP  - X ■ ^ ,tVV.i'J  ,,  ;.  V .'W  V'^' 

W'  ^ > -ii/tB  .XH  .,7 ••c^eiSfc '•feo^^riaiiiiL 

*,.-»V'\.  ’ ‘ U-*’-  I * '••»:,  • .s^  ' 

oXJ  ^ , .api*i|.,Xoo  tf  ■HniVMfH: 

' ‘ yr.  t A ^ .■*  ^'i(^»r^irv  A.J1  *A  if  j*  i ft.  . jC  «-  * _i._  i «.  ..fti,  ._  . L, 


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fr?3!^«tsc.*r:awi; 


29 


The  iodine  was  thought  responsible  for  this  conduct  in  having 
added  to  form  a pentavalent  arsenic  compound.  Hence  the  entire 
experiment  was  repeated  using  ethyl  bromide  instead  of  iodide. 

The  ether  layer  was  v/ashed  with  v;ater  and  dilute  NaOH  to  remove 
magnesium  salts  and  HE.r,  dried  with  CaCl2^  and  distilled  as  be- 
fore, ^n  this  case  much  closer  boiling  range  was  observed,  the 
maximum,  being  220--230°  v/ith  by  far  the  greater  part  of  it  going 
over  at  223--225*^;  yield  12.5  grams.  The  distillate  v/as  added 
to  1.5  mols  of  ethyl  iodide  in  a pressure  tube  and  heated  on  a 
steam  bath  several  hours.  Vi'hen  first  mixed  the  solution  Vi/as 
clear,  colorless,  and  homogeneous,  but  became  turbid  in  a minute 
or  so.  After  heating  for  an  hour  on  the  steam  bath,  half  the 
contents  of  the  tube  were  solid;  in  another  hour  it  was  nearly 
all  solid.  The  solid  product  was  found  to  be  too  soluble  for 
satisfactory  recrystallization  from  v;ater,  alcohol,  chloroform, 
ether,  and  butyl  alcohol.  It  was  found,  however,  to  crystallize 
well  from  a mixture  of  2 parts  of  benzene  to  1 of  acetone,  from 
which  it  v;as  obtained  in  beautiful  hard,  granular,  v/hite  crystals 
of  prism  formation.  It  melted  sharply  at  104°, 

Subs.,  0.2826,  0.2394:  27.80,  23.60  cc.  Iodine 

(Icc,  r 0.001963  g.  As) 

Calc,  for  CgH5As(C2l%)3l;  As,  20.49^o 
Calc,  for  CgH3As(C2Hg)3l.H20:  As,  19.53^ 

Found,  19.31,  19.35^ 

With  n- Propyl  Bromide . 

Phenylarsine  (16  g)  v/as  converted  to  the  Grignard  complex 
and  to  it  v;as  added  26  grams  of  n-propyl  bromide  (2  mols)  . The 
reaction  went  smoothly,  the  m.ixture  v/arming  up  appreciably. 


30 


The  mixture  was  decomposed  v/ith  ice  and  dilute  H2S0^  as  before. 

The  ether  fraction  was  vacuum  distilled,  boiling  at  138--140°/25  mm 
A yield  of  10  g.  phenyl -dipropyl  arsine  was  obtained.  A portion 
of  it  (5  g)  was  mixed  with  5 g.  n-propyl  iodide  and  heated  in  a 
pressure  tube  on  a steam  bath  for  3 hours.  It  had  changed  to 
a heavy  darjc  colored  oil  v/hich  solidified  on  cooling  to  a soft 
mass  of  crystals.  This  material  was  found  to  crystallize  well 
from  the  benzene  acetone  mixture  used  before,  and  appeared 
similar  to  the  analogous  ethyl  compound:  m.p.  168°. 

Subs.  0.3182,  0.2750:  Iodine  29,54,  25.51 

(1  cc.  iodine  = 0.001963  g.  As) 

Calc,  for  GQll^As{C^Er^)^l:  As,  18.38^ 

Found,  18.22,  18.21^^ 

With  n- Butyl  Iodide . 

Phenylarsine  (16  g)  was  converted  to  the  Grignard  complex  and 
to  it  was  added  two  mols  of  n-butyl  iodide.  No  reaction  was 
apparent,  the  heavy  dark  layer  below  the  ether  remaining  unchanged 
in  appearance.  The  mixture  was  refluxed  over  steam  for  half  an 
hour  and  allowed  to  cool;  the  liquid  appeared  to  be  homogeneous, 
but  after  standing  for  some  time  tv/o  layers  v/ere  apparent. 

They  were  nearly  the  same  color,  light  amber  yellow,  in  contrast 
with  the  almost  opaque  greenish  layer  of  Grignard  complex. 

After  treatment  as  before  the  ether  fraction  was  vacuum  distilled; 
b.p.  173--175°/38  ram.  Yield  15  g.,  55^. 

A portion  of  the  distillate  (5  g)  V\ras  mixed  vath  5 g.  of  n- 
butyl  iodide  in  a pressure  tube.  After  heating  two  hours  in  a 
steam  bath  a little  heavy  dark  oil  appeared  in  the  bottom  of  the 


.n 


r 


ro 


* • • < 
V ’ - -■*. 


' ^ w 

'!  ■;  N ^ .. 


•‘  '. '.»  w ' l.ii} 


, Mi.  ' . ^ >,  ■" ' '•  • ’ (i^ul., 

^ /•'  ^*  - .rXc '?  *-  ':  i'- 

‘ ix  <'M  ,f  o t 


^ . I , I Ij.f  t' 


'4 

K* 


.7' 


.’  -‘  r ■.  *'■  ■ ' I 


\ V 


• dr-u. 

• i'. 


31 


mixtiAre . Heating  24  hours  more  converted  the  entire  mixture  to 
the  dark  oil,  which  on  cooling  solidified  into  a mass  of  soft 
crystals.  The  material  v;as  twice  crystallized  from  benzene, 
from  which  it  separated  in  white,  thin  flakes  resembling  benzoic 
acid;  m.p.  140°,  yield  4.5  g. 

Subs.,  0.2492:  Iodine  20.97  (lc5?.  = 0.001963  g.  As) 

Calc,  for  CgHgAs(C^Hg)2l:  As,  16.67.  Found  16.52 

An  attempt  was  made  to  analyse  these  three  arsoniiim  iodides 
for  iodine  boiling  up  with  an  excess  of  standard  AgNO^  and 
titrating  w ith  iTH^CNS,  using  ferric  alum  as  an  indicator  as 
suggested  by  Behn  (3).  But  the  method  v/as  found  impractical 
because  of  coloration  difficulties  which  masked  the  end-point 
completely.  In  one  instance  the  first  addition  of  thiocyanate 
produced  a deep  violet  coloration. 

With  Benz aldehyde . 

Phenylarsine  (17  g)  was  converted  to  the  G-rignard  complex 
and  to  it  v;as  added  two  mo  Is  of  benzaldehyde  dissolved  in  anhy- 
drous ether.  A decided  evolution  of  heat  occurred  and  the  solu- 
tion became  heavily  turbid.  The  heavy  oily  layer  under  the 
ether  did  not  change  in  appearance,  however,  even  after  prolonged 
and  vigorous  shaking.  Ice  and  dilute  were  added  and  the 

ether  layer  separated.  A yellow  crystalline  material  soon 
began  to  separate  from  the  ether  and  continued  coming  out  for  a 
couple  of  days.  It  was  identified  as  arsenobenzene  by  mixed 
melting  point.  Evidently  the  phenylarsine  had  not  reacted. 

With  Chloracetic  Ester. 


Phenylarsine  (16  g)  was  converted  to  the  Grignard  complex 


1 


32 


and  to  it  v/as  added  two  mols  of  chloracetic  ester.  The  reaction 
v/as  vigorous  and  required  to  be  cooled  with  ice.  Solid  light 
yellow, material  separated  from  the  mixture.  On  decomposing  w ith 
ice  and  dilute  HgSO^  considerable  of  the  solid  was  present  and 
v;as  filtered  out.  Several  crops  v/ere  similarly  obtained  before 
no  more  finally  appeared.  The  material  v/as  identified  as  arseno- 
benzene  by  mixed  melting  point. 


Phenylarsine  (10.5  g)  was  converted  to  the  Orignard  complex 
and  to  it  v/as  added  15.7  g.  (1  mol)  of  ethylene  bromide.  Little 
heat  was  evolved,  and  a light  colored  solid  appeared.  The 
appearance  of  the  mixture  v/as  not  noticeably  changed  after  re- 
fluxing for  an  hour.  -^fter  decomposition  v/ith  ice  and  dilute 


Practically  nothing  was  left  after  evaporating  off  the  ether. 

The  solid  v/as  identified  as  arsenobenzene  by  mixed  melting  point. 


Phenylarsine  (11.4  g)  v/as  converted  to  the  Grignard  complex 
and  to  it  v/as  added  10. 6 g.  (1  mol)  of  dichloroethyl  et?ner. 
Shortly  a reaction  began  causing  the  ether  to  boil.  A pale 
yellow  solid  appeared  in  the  mixture  and  on  standing  considerable 
more  appeared.  After  adding  ice  and  dilute  HgSO^  the  solid  v/as 
filtered  out.  On  standing  more  solid  appeared  in  the  ether 
fraction  and  v/as  filtered  oiit . It  v/as  identified  as  arsenoben- 
zene by  m.ixed  melting  point. 

■’’.^ith  Pent amethylene  Bromide  . 

Phenylarsine  (14.6  g)  was  converted  to  the  Grignard  complex 


P/ith  Ethylene  Bromide . 


^s'^^4  solid  was' filtered  out  and  the  ether  layer  separated. 


and  to  it  v/as  added  21.8  g.  (1  mol)  of  pentamethylene  bromide. 


33 


The  reaction  proceeded  vigoroiisly.  After  decomposing  with  ice 
and  dilute  the  ether  fraction  v;as  vacuum  distilled.  A 

small  amount  of  material  (about  4 grams)  passed  over  at  160-- 
170°/30mm,  A mercuric  chloride  derivative  prepared  in  alcoholic 
solution  m.elted  over  considerable  range  even  after  several  re- 
crystallizations from  alcohol,  and  15--20  degrees  lower  than  the 
mercuric  chloride  derivative  of  arsepedine  (20). 

The  reaction  was  repeated  in  the  cold  with  stirring,  using 
15,1  g.  of  phenylarsine . The  ether  extract  distilled  over  con- 
siderable range  and  amounted  to  about  10  gram.s  of  impure  material 
( 150--200°/35--40  mm.).  On  standing,  the  distillate  became  half 
solid  withv/hite  coarsely  crystalline  material,  which  was  re- 
crystallized  from  a mixture  of  acetone  and  benzene;  transparent, 
granular  cubes  and  prisms,  m.p.  161--162^.  The  m.aterial  w^as 
readily  sol’ble  in  v/ater,  giving  a distinct  acid  reaction  to  lit- 
mus paper, 

Tubs.  0,2071,  0.2403:  Iodine  25.09,  29.10 

(1  cc . iodine  - 0.001965  g.  As) 

Calc,  for  (CgH5)Br(CH2)5As0(0H)  ; As  23.51?^ 

Found,  23.78,  23.77f^ 

The  STibstance  gave  a decided  test  for  halogen  by  the  copper 
v.'ire  miethod, 

With  Allyl  Bromide . 

Phenylarsine  (21.9  g)  was  converted  to  the  3-rlgnard  complex 
and  to  it  was  added  34.4  g.  (2  m.ols)  allyl  bromide.  The  reaction 
was  carried  on  in  a two-necked  flask  provided  w ith  a stirrer  and 
a reflux  condenser.  The  flask  was  surrounded  with  salt  and  ice 
and  the  allyl  bromide  was  added  dropv/ise  through  the  condenser. 


34 

Considerable  light  yellow  solid  appeared  during  the  reaction 
which  was  identified  as  ar s e nob en zone  by  mixed  melting  point. 

The  ether  layer  yielded  about  1 cc,  of  heavy  oil  after  evaporating 
off  the  ether, v/hich,  distilled  v/ith  decorapos.it ion. 

VJith  Benzyl  Chloride . 

Phenylarsine  (20.5  g)  v/as  converted  to  the  Grignard  complex 
and  to  it  was  added  34  g.  ( 2 mols)  of  benzyl  chloride  in  the  f 

cold  v;ith  stirring.  After  adding  ice  and  water  and  separating 
the  ether  layer,  a white,  finely  crystalline  materia  1 b egan  to 
separate  from  the  ether  solution.  This  white  solid  continued 
to  form  for  several  days,  when  the  ether  solution  remained  clear 
on  filtering. 

The  solid  was  found  to  be  soluble  in  dilute  alkali  and  pract- 
ically insoluble  inv/ater,  hot  or  cold.  It  v/as  therefore  dissol- 
ved in  dilute  NaOH,  filtered  (although  it  was  almost  entirely 
dissolved),  acidified,  fi Itered  v; ith  suction,  v/ashed  v/ith  water, 
and  sucked  as  dry  as  possible.  It  v;as  found  to  crystallize 
beautifully  from  hot  alcohol,  frora  which  it  separated  in  fine, 
white,  glistening  needles:  m.p.  196--197‘^. 

Subs.  0.3415:  Iodine,  46.45  cc.  ( 1 cc.  = 0.001963  g.  As) 

Calc,  for  CgH5CH2(CgH5)AsOOH:  As,  27.17^ 

Found:  As,  26.70^ 

The  experiment  was  repeated  vrith  20.2  g.  phenylarsine. 

•Fwice  the  theoretical  amount  of  benzyl  chloride  (66.5  g.,  4 mols) 
was  added  v/ith  stirring  at  room  temperature.  On  the  addition  of 
ice  and  dilute  HgSO^  a v^hite  solid  immediately  precipitated  and 
v;as  filtered  out.  It  was  fo\md  to  crystallize  well  from  hot 
water,  coming  down  in  fine  white  needles:  m.p,  142--143'^.  It 


35 


did  not  appear  any  more  soluble  in  weak  alkali  than  in  v/ater. 

Subs.  0,2687:  ^odine  21.85  (1  cc.  = 0.001963  g.  As) 

Calc,  for  0'gH5(Cgil5CH2)3AsCl:  As,  16.29,^ 

Found  15 . 96/j 

A voluminous  yield  of  phenylbenzylarsinic  acid  very  slowly 
separated  from  the  ether  solution  as  in  the  first  case. 

With  Aromat Ic  Halides : Brombenzene . 

Phenylarsine  (19.4  g)  was  converted  to  the  Orignard  c omples 
and  to  it  was  added  2 mols  of  brombenzene.  As  no  reaction  y/as 
apparent  the  mixture  was  refluxed  several  hours  v;ith  stirring. 
After  adding  ice  and  dilute  HgSO^  the  ether  layer  v;as  found  to 
contain  the  unreacted  phenylarsine  and  brombenzene . For,  after 
allov;ing  the  phenylarsine  to  oxidize  to  arsenobenzene,  filtering, 
and  distilling  the  ether  extract,  the  boiling  point  was  found  to 
coincide  with  that  of  brombenzene. 

7/ith  p-Chloronitrobenzene . 

Phenylarsine  (16.1  g)  v/as  converted  to  the  Grignard  c omplex 
and  to  it  v/as  added  two  mols  of  p-ohloronitrobenzene  dissolved  in 
dry  ether.  The  mixture  v/as  cooled  with  ice  and  stirred.  Con- 
siderable arsenobenzene  v/as  formed  diiring  the  reaction,  and  more 
appeared  in  the  ether  solution  after  decomposing  with  ice  and 

dilute  H2S0^  and  separating  the  layers.  No  basic  amino  compound 
was  found;’ on  making  the  aqueous  fraction  alkaline  and  shaking  out 
with  ether.  Consequently  the  nit ro  group  v/as  not  reduced  to  an 
amino  group.  An  ether  soluble  material  (containing  no  arsenic) 
was  found  in  the  ether  fraction  along  v/ith  unreacted  p-chloro- 
nitrobenzene , from  which  it  v/as  separated  by  several  crystalli- 
zations from  alcohol;  it  was  soft,  orange  colored  material; 


36 

softens  and  melts  170--176®.  4, 4 ’ -dichloroazobenzene  melts  at 

163--184°  (Richter). 

Further  Study  of  the  Reaction  with  Ethyl  Bromide . 

An  attempt  was  made  to  find  optimum  conditions  for  the  for- 
mation of  the  tertiary  arsine  by  altering  the  factors  of  heat  and 
mass  relationship. 

(1)  Phenylarsine  (18.5  g)  was  converted  to  the  Grignard 
complex  and  to  it  v/as  added  26.2  g.  (2  mols)  of  ethyl  bromide. 

The  reaction  mixture  v;as  cooled  v;ith  ice  and  stirred  for  an  hour 
after  the  materials  were  mixed.  Without  allowing  to  warm  up, 
the  mdxture  was  treated  with  dilute  Il2S0^  as  usual.  The  ether 
v/as  evaporated  under  vacuumi;  on  admission  of  air  the  contents  of 
the  flask  became  warir^  and  entirely  solidified.  Some  of  the 
solid  was  recrystallized  from  benzene  and  identified  as  arseno- 
benzene  by  a mixed  melting  point. 

(2)  Phenylarsine  (17,5  g)  v/as  treated  as  above,  except  that 
before  adding  ice  and  dilute  H2S0^  it  was  gently  refluxed  for 
half  an  hour.  The  ether  layer  was  allov/ed  to  stand  for  some  time, 
v/hereupoh  yellov/  needles  of  arsenobenzene  separated  o\it.  On 
evaporating  the  ether,  a small  amount,  perhaps  2 cc.  of  the  ter- 
tiary arsine  remained. 

(3)  Phenylarsine  (18.3  g)  v/as  similarly  treated  v/ithout 
cooling  or  refluxing,  and  twice  the  theory  (4  mols)  of  ethyl 
bromide.  Stirring  was  continued  an  hour  after  mdxing  the  ma- 
terials. After  the  usual  treatment  the  ether  fraction  v/as 
evaporated  under  vacuum.  The  residual  oil  v/armed  up  somev/hat 
on  admission  of  air,  but  no  solid  appeared;  it  was  vacuum  dis- 
tilled, and  redistilled.  A fraction  was  taken  at  125--130°/25mm. 


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37 

and  a small  high  boiling  residue  remained.  The  distillate 
weighed  11  g, , 4:5%  yield. 

It  is  evident  tt  least  that  cooling  hinders  the  reaction 
almost  completely,  and  that  the  best  yield  is  obtained  at  room 
temperature  v;ith  excess  of  ethyl  bromide. 

Attempt  to  make  the  G-rignard  Complex  of  Phenylar s ine 
from  Phenylar sine  Dichloride . 

Phenylarsine  dichloride  (22  g)  was  dissolved  in  anh^^-drous 
ether  and  t o it  was  added  2 mols  of  magnesium.  Wo  reaction  took 
place,  although  the  mixture  was  refluxed  several  hours,  and  a few 
crystals  of  iodine  and  a little  separately  prepared  Grignard 
reagent  were  added. 


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38 


V.  SUMYARY 

1.  It  v/as  fo-ond  impossible  to  prepare  acetylated  or  benzoy-  .• 
lated  derivatives  of  phenylarsine  analogous  to  the  anilides; 
either  no  reaction  occurred  at  all,  or  the  phenylarsine  was  par- 
tially oxidized  to  arsenobenzene . 

2,  An  attempt  to  condense  phenylarsine  with  an  aromatic 
nitroso  compound,  splitting  out  a molecule  of  water  and  forming 
a linkage  of  the  type  -As:U-  was  unsuccessful.  Evidence  points 
to  the  formtion  of  an  anilide  of  an  ar sonic  acid,  containing  the 


group: 


0 

-As-!'^H- 

OH 


3.  The  phenylarsine-Gr ignard  complex  formed  by  adding  an 

alkyl  Grignard  reagent  to  phenylarsine  was  found  to  offer  a means 
of  attaching  various  groups  to  the  arsenic  through  the  use  of 
certain  halogenated  substances  by  a reaction  of  the  type. 


C 


6H5AS 


MgX 


MgX 


2 RX  = CgllgAsRg  t 2 MgXg. 


4.  Through  the  phenylarsine -Grignard  complex  both  one  and 
tvi/o  hydrocarbon  groups  were  attached  to  the  arsenic,  forming 
secondary  and  tertiary  mixed  arsines. 

5.  Attempts  to  form  ring  structures  including  the  arsenic 
by  the  use  of  dihalogenated  compounds  were  unsuccessful. 

6.  Aromatic  compounds  containing  the  halogen  in  the  benzene 
nucleus  would  not  react  with  the  phenylarsine -Grignard  complex. 


59 


VI.  BIBLIOGRAPHY 

(1)  The  Reactions  of  the  Arsines,  Preliminary  paper.  Con- 

densation of  Primary  Arsines  with  Aldehydes.  Roger 

Adams  and  C.  S.  Palmer.  J.  Am.  Chem.  Soc.  2375 

(1920) 

(2)  Palmer,  Ber.  1378  (1894) 

(3)  Dehn  and  Wilcox,  Am.  Chem.  J.,  1--54  (1906) 

(4)  Palmer  and  Dehn,  Ber.  M,  3594  (1901) 

(5)  La  Coste  and  Michaelis,  Ann.  201,  203  (1880) 

(6)  Michaelis  and  Loesner,  Ber.  27,  264  (1894) 

(7)  Norris,  J,  Ind.  and  Eng.  Chem.  IJ,  824  (1919) 

(8)  Dehn,  Am.  Chem.  J.,  101  (1905) 

(9)  Dehn,  Am.  Chem.  J.,  88  (1908) 

(10)  D.R.P,  254.187 

(11)  D.R.P.  251,104 

(12)  D.R.P.  253,226 

(13)  D.R.P.  270,254 

(14)  D.R.P.  269,699 

(15)  D.R.P.  269,700 

(16)  D.R.P.  269,743 

(17)  D.R.P.  269,744 

(18)  D.R.P.  269,745 

(19)  Estimation  of  Arsenic  in  Organic  Compomds . G.  R.  Robertson. 

J.  Am.  Chem.  Soc.,  43,  182  (1921) 

(20)  Organic  Compounds  of  Arsenic  and  Mercury.  G.  T.  Morgan. 


\ r 


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VITA 


40 

The  v/riter  was  horn  in  Sullivan,  Illinois,  January  3,  1893, 
and  obtained  his  early  education  at  that  place,  graduating  from 
the  Sullivan  High  School  in  1912.  The  follov/ing  year  he  took 
post  graduate  v/ork  in  high  school  and  filled  the  position  of  as- 
sistant in  the  science  department.  He  entered  the  University 
of  Illinois  in  1914,  choosing  the  course  in  Chemical  Engineering, 
and  graduated  in  1919.  He  received  the  degree  of  Master  of 
Science  in  Chemistry  in  1921. 

Appointments : 

Scholarship,  University  of  Illinois,  1919--20. 

U.  S.  Interdepartmental  Social  Hygiene  Board  FelloVifship, 
University  of  Illinois,  1920--21. 

Fellowship,  University  of  Illinois,  1921--22. 

Fiiblications : 

Transference  Nurrbers  of  Sodium  and  Potassium  in  Mixed 
Chloride  Solutions.  With  S.  A.  Bra ley.  J.  Am. 
Chem.  Soc.  1770  (1920) 

On  the  Electrical  Properties  of  Illium.  With  Charles 
T.  linipp.  The  Physical  Reviev/,  19,  283  (1922) 


